Patent GB-794380-A (GB)
Title: Improved oils
Inventor: AIRS RAYMOND SPENCER
IPC: F02B3/06
Filed: 1956-02-06
Abstract: Alkanolamine esters of boronic acids, R1B(OH)2, and borinic acids, R1,R2,BOH are added to fuel and lubricating oils (see Group III). The groups R1 and R2 contain at least three carbon atoms and may be aliphatic, cycloaliphatic, aromatic or heterocyclic and either may contain one or more substituents such as alkoxy, esterified carboxyl, hydroxyl, amino, nitrile, nitro, or boromic or borinic acid groups or halogen atoms.  Preferred acids are benzyl, phenyl and tolyl boronic and dibenzyl, diphenyl and ditolyl borinic acids and phenylene-1,4- and naphthalene-1,4-diboronic acids.  Suitable alkanolamines are mono-, di-, and triethanolamine, the amino-propyl alcohols and their N-dimethyl and N-diethyl derivatives and the amino butyl alcohols. Particularly preferred alkanolamines are N-hexyl, N-decyl, N-dodecyl and N-octadecyl ethanolamines and N-hexyl and N-octadecyl diethanolamines.  The esters may be prepared by the azeotropic esterification of the acid or its anhydride with the alkanolamine in molar proportions in the presence of a suitable water entrainer which may also act as solvent, e.g. benzene or toluene.  In examples, the preparation is described of (i) 3-azapentamethylene phenylbozonate from phenylboronic acid and diethanolamine in toluene solution; (ii) bis-(2-aminoethyl) phenylboronate from phenylboronic acid and ethanolamine in benzene solution; (iii) 2-aminoethyl diphenylborinate from diphenylborinic acid and ethanolamine in methylated spirits solution; (iv) N - hexyl - 3 - azapentamethylene phenylboronate from N-hexyl diethanolamine and phenylboronic acid in benzene solution, and (v) an N-tertiary alkyl ethanolamine ester of diphenyl borinic acid in xylene solution.ALSO:Oil compositions comprise a major proportion of an oil and a minor proportion of an ester of an alkanolamine and a boronic or borinic acid containing a group having at least three carbon atoms attached to the boron atom by a carbon to boron linkage. The oil may be of any type, e.g. hydrocarbon fuel, lubricating, and electrical oils, fatty oils and synthetic oils. Examples of suitable oils include straight-run, reformed, cracked or polymerized gasolines, or blends of gasolines with one another or with volatile alcohols or ethers, benzene, mixtures of aromatic hydrocarbons, such as benzene and toluene, naphthas, aviation turbine fuels, kerosines, diesel fuels, gas oils, or mixtures of two or more of these fuels; mineral lubricating oils, fatty oils and synthetic lubricating oils, e.g. polymerized olefines, polyoxyalkylene compounds, silicones and esters such as di-(2-ethyl hexyl) sebacate and trioctyl phosphate.  Suitable alkanolamines are mono-, di-, and triethanolamine, 2-aminopropyl alcohol, 3-aminopropyl alcohol and its N-dimethyl and N-diethyl derivatives and the amino butyl alcohols, the preferred compounds being the N-alkyl (especially C6-24 alkyl) derivatives of mono- and dialkanolamines, e.g. N-hexyl mono- and diethanolamine, N-decyl ethanolamine, N-dodecyl ethanolamine, N-octadecyl ethanolamine and N-octadecyl diethanolamine.  The boron acids have the general formula <FORM:0794380/III/1> when R1 is a group having at least 3 carbon atoms and R2 is an organic group, both being attached to the boron atom by a carbon to boron linkage.  R1 and R2 may be aliphatic, cycloaliphatic, aromatic or heterocyclic groups and either may contain one or more substituents such as methoxy, ethoxy, esterified carboxyl, hydroxyl, amino, nitrile, nitro, boronic or borinic acid groups or halogen atoms.  Examples of suitable boronic and borinic acids are those where R1 and/or R2 are propyl, butyl, octyl, decyl, hexadecyl, octadecyl, heptadecenyl, benzyl, phenyl, methyl phenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, chlorophenyl, methyl chlorophenyl, nitrophenyl, benzoylaminophenyl, naphthyl, methylnaphthyl, methoxynaphthyl, chloronaphthyl, nitronaphthyl, aminonaphthyl, tolyl, fluorenyl, anthryl, phenanthryl, pyridyl, picolyl, pyrrolyl, indolyl, carbazolyl, furyl, benzofuranyl, or dibenzofuranyl, the aromatic boronic and borinic acids such as benzyl boronic, dibenzyl borinic, phenyl boronic, diphenyl borinic, tolyl boronic and ditolyl borinic acids being preferred. Arylene di-boronic or di-borinic acids may also be used, e.g. phenylene- or naphthalene-1,4-diboronic acid. Examples of suitable esters of the boron acids are those derived by esterifying diethanolamine with phenylboronic, p-tolyl boronic, p-methoxyphenylboronic, p-bromophenyl boronic or m-nitrophenyl boronic acid.  Details are given of the preparation (see Group IV (b)) of : (i) 3-azapentamethylene phenylboronate; (ii) bis - (2 - aminoethyl) phenylboronate; (iii) 2 - aminoethyl diphenylborinate; (iv) N-hexyl-3-azapentamethylene phenylboronate; and (v) the diphenyl borinic ester of a commercial N-t-alkyl ethanolamine.  Optional ingredients are lead tetralkyls (ethyl and/or methyl) and antioxidants such as dimethyl-6-t-butyl phenol, 2,6 - di - t - butyl - 4 - methyl phenol, N - phenylalpha - naphthylamine and N,N1 - dibutyl - p - phenylene diamine. In examples a petroleum hydrocarbon fraction of boiling range 80-100 DEG  C. is treated with above-mentioned esters (iv) and (v).